Production of assistants for the



Patented Feb. 22, 1938 UNITED STATES PATENT QFFECE PRODUCTION OF ASSISTANTS FOR THE TEXTILE AND RELATED INDUSTRIES the-Main, Germany No Drawing. Application May 21, 1935, Serial No. 22,584. In Germany May 30, 1934 6 Claims.

The present invention relates to new assistants in the textile and related industries, especially as wetting, washing, dispersing and like agents and a process for producing same.

We have found that valuable wetting, washing, dispersing and like agents can be obtained by sulphonating mixtures of products boiling above 200 C. obtained from mineral coals, such as mineral coal tars, or hydrogenation products of mineral coals or mineral coal tars or dehydrogenation products of the same.

Especially suitable initial materials are the fractions boiling above 200 C. of the products obtained by the destructive hydrogenation of mineral coals or mineral coal tars while employing superatmospheric pressure for example according to the processes described in Australian Patent No. 1217/26. The said fractions may again be separated into single fractions and/or freed from certain nuclear compounds of high molecular weight, such as naphthalene, anthracene, pyrene, chrysene and fluorene, by cooling or extraction with solvents. Also the pitch fractions boiling above 400 C. obtainable by the distillation of mineral coal tars or of the said hydrogenation products boiling above 200 C. or the dehydrogenation products thereof are suitable as initial materials. The said pitch fractions are advantageously extracted with solvents, such as carbon disulphide or alcohol, the residue obtained being sulphonated.

The dehydrogenation of the hydrogenation products of mineral coals or mineral coal tars is carried out by heating the hydrogenation product at temperatures of between 300 and 600 C. in the presence of catalysts, for instance as it is described for example in U. S. Patents 1,913,940 and 1,975,476.

In the present process the sulphonation of the initial materials is effected by employing concentrated sulphuric acid, oleum, sulphur trioxide or chlorsulphonic acid, if desired with an addition of agents combining with water, such as acid anhydrides or acid chlorides, as for example phosphorus pentoxide or acetic anhydride. The temperature to be employed for the sulphonation depends on the nature of the initial materials and the nature of the sulphonating agents. Ordinary or increased temperatures, as for example from to 200 C., may be employed. When employing products containing a considerable amount of unsaturated hydrocarbons, preferably the dehydrogenation products of mineral coal tars, etc., the sulphonation can usually be carried out while using mild reaction conditions, for example employing temperatures between 10 and 50 C. When products are employed which contain no or only a relatively small amount of unsaturated hydrocarbons it is preferable to employ high temperatures. The sulphonation is carried on until the reaction product is partially or Wholly soluble in water.

The crude sulphonation products obtained are freed from the excess of sulphonating agent and preferably also from unsulphonated and unsulphonatable constituents, neutralized with alkalies, ammonia or amines and the resulting solutions evaporated, if desired to dryness. Watersoluble products are obtained which have a high wetting, washing and dispersing power. When dark colored sulphonation products are obtained, they may be rendered lighter in color by treatment with bleaching earths, animal carbon or sodium hypochlorite solution.

The sulphonation products obtained according to the process as described may be employed advantageously for wetting and washing textiles even in acid baths, furthermore for the preparation of emulsions suitable for impregnating textile materials, leather, paper and the like. Such products as are dark colored may be employed for the preparation of emulsions of bituminous substances.

The following example will further illustrate the nature of this invention but the invention is not restricted to this example.

20 parts of ground mineral coal yielding considerable amounts of gases and burning with large flame (so-called Gasflammkohle) are impregnated with an amount of hydrochloric acid sufiicient to neutralize their alkalinity, dried and triturated to a paste of high consistency with 10 parts or" fused soft pitch (derived from a mineral coal hydrogenation product) having a setting point of 50 C. with an addition of 1 part of ferric oxide gas purifying mass impregnated with ammonium molybdate solution, the temperature being C. The paste is pumped at a temperature of 150 C. through a short wide pipe into and through a pressure-tight reaction vessel provided with a stirrer and hydrogenated therein at 500 C. with hydrogen under a pressure of atmospheres, the reaction materials remaining in the reaction chamber for 20 minutes. After removing the solid ash and coal constituents by centrifuging, the hydrogenation product is distilled to hard pitch with superheated steam under reduced pressure, the oil passing over above 250 C. at 50 millimeters (mercury gauge) being distilled again at the same pressure. When the fraction boiling tion from hot water.

between 250 and 280 C. at the said pressure is allowed to stand, pyrene separates in an amount of 1 per cent of the coal employed.

Example After removing the separated pyrene, the oily product obtained is subjected to fractional distillation and the pitch fraction boiling above 400 C. is extracted in the cold with carbon disulphide. The residue which remains is sulphonated by treatment for two hours with 20 per cent of its weight of 98 per cent sulphuric acid while stirring at 200 C. The reaction mixture is treated with water and freed from acid resin formed by centrifuging. lhe product obtained in this manner is neutralized with caustic potash solution and then toa great extent evaporated. A crystal pulp is obtained which is crystallized from hot water for the purpose of purification. The resulting product has a high wetting power.

The carbon disulphide extract is freed from solvent by distillation and the resulting residue sulphonated in the manner already described after separation of the pyrene and chrysene contained therein. The aqueous solution of the sulphonation product is treated with a cold saturated solution of potassium chloride or caustic potash, the resulting potassium salt of the sulphonation product being purified by crystalliza- This product also has a good wetting and dispersing action.

What we claim is:-

1. A process for the manufacture of assistants for the textile and related industries which comprises sulphonating at temperatures of befor the textile and related industries which comprises sulphonating at temperatures of between about 10 and about 200 C. a product obtained by dehydrogenating a product boiling above 200 C. and obtained by hydrogenating a material selected from the group consisting of mineral coals and mineral coal tars.

3. A process for the manufacture of assistants for the textile and related industries which comprises sulphonating at temperatures of between about 10 and about 200 C. a product boiling above 200 C. and obtained by hydrogenating a material selected from the group consisting of mineral coals and mineral coal tars which have been freed from condensed polycyclic compounds of high molecular weight by extraction with organic solvents.

4. Sulphonation products obtainable by sulphonation at temperatures of between about 10 and about 200 C. of a product boiling above 200 C. and obtained by hydrogenating a material 'selected from the group consisting of mineral coals and mineral coal tars.

5. Sulphonation products obtainable by sulphonation at temperatures of between about 10 and about 200 C. of a dehydrogenation product of a product boiling above 200 C. and obtained by hydrogenating a material selected from the group consisting of mineral coals and mineral coal tars.

6. A process for the manufacture of assistants for the textile and related industries which comprises causing a sulphonating agent at a temperature between about 10 and about 200 C. to act on a product boiling above 200 C. and obtained by a process comprising hydrogenating a material selected from the group consisting of mineral coals and mineral coal tars.

MATHIAS PIER. BRUNO ENGEL. 

